EP0176456B1 - Procédé de préparation de O alcoyle S (alcoyle ramifié en alpha) alcoyl phosphonothioate - Google Patents
Procédé de préparation de O alcoyle S (alcoyle ramifié en alpha) alcoyl phosphonothioate Download PDFInfo
- Publication number
- EP0176456B1 EP0176456B1 EP85420165A EP85420165A EP0176456B1 EP 0176456 B1 EP0176456 B1 EP 0176456B1 EP 85420165 A EP85420165 A EP 85420165A EP 85420165 A EP85420165 A EP 85420165A EP 0176456 B1 EP0176456 B1 EP 0176456B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- process according
- alpha
- reaction
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 24
- -1 alkyl phosphonothioates Chemical class 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title description 9
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000004820 halides Chemical class 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229960004979 fampridine Drugs 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 101100372602 Arabidopsis thaliana VDAC3 gene Proteins 0.000 abstract 1
- 230000000749 insecticidal effect Effects 0.000 abstract 1
- 230000001069 nematicidal effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WOHOOQZHIVDEMO-UHFFFAOYSA-N 2-[ethoxy(ethyl)phosphoryl]sulfanyl-2-methylpropane Chemical compound CCOP(=O)(CC)SC(C)(C)C WOHOOQZHIVDEMO-UHFFFAOYSA-N 0.000 description 1
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HZBFWRKXQNPMER-UHFFFAOYSA-N C(C)P(=S)(Cl)[ClH]CC Chemical compound C(C)P(=S)(Cl)[ClH]CC HZBFWRKXQNPMER-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000135309 Processus Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HJKNCRRBGPFVJW-UHFFFAOYSA-N ethoxy-hydroxy-sulfidophosphanium Chemical compound CCOP(O)=S HJKNCRRBGPFVJW-UHFFFAOYSA-N 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical class SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- FUWGSUOSJRCEIV-UHFFFAOYSA-N phosphonothioic O,O-acid Chemical class OP(O)=S FUWGSUOSJRCEIV-UHFFFAOYSA-N 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
Definitions
- the present invention relates to a new process for the preparation of O-alkyl S- (alpha branched alkyl) alkyl phosphonothioates.
- Some of these compounds are known for their interesting insecticide and nematicide properties which can be used for crop protection.
- French application 2516517 relates to the preparation of O-alkyl-S (tertioalkyl) alkylphosphonomonothioate compounds by reaction of a halide of an S- (tertioalkyl) alkyl-phosphonothioic acid on an alcohol or phenol in the presence of a base, according to the diagram :
- This process is carried out with a yield of around 70% but makes it possible to obtain the products considered using a global process in four stages from a trialcoylphosphite.
- the present invention relates to a new process for the preparation of these products which can be used as the last step of a global process in three steps, therefore simplified and easier to implement on an industrial scale.
- the reaction is advantageously carried out at a temperature between 0 ° C and 100 ° C.
- a high temperature does not promote a good yield, this is why one preferably works between 15-50 ° C and for convenience at room temperature.
- the acid acceptor can be a strong organic base such as a tertiary amine, such as a trialkylamine, for example triethylamine or ethyldiisopropylamine or a pyridine such as pyridine and dimethylaminopyridine.
- a strong organic base such as a tertiary amine, such as a trialkylamine, for example triethylamine or ethyldiisopropylamine or a pyridine such as pyridine and dimethylaminopyridine.
- This organic base is advantageously used in a substantially stoichiometric amount.
- the acid acceptor according to the invention must be combined with a minor amount of auxiliary base.
- the auxiliary base combined in an amount of 0.5 to 15% and preferably from 1 to 10%, is an organic base with a pk a at least equal to that of dimethylamino-pyridine and different from the first.
- a dialkoyl- or alkyleneaminopyridine the whole of the alkyl part containing from 1 to 6 carbon atoms, and in particular 4-pyrrolidino-pyridine and preferably 4-dimethylamino-pyridine.
- organic solvents there may be mentioned aliphatic hydrocarbons such as cyclohexane, optionally chlorinated such as methylene chloride, ketones such as 2-butan, aromatic solvents such as benzene, toluene, xylene.
- the reaction is carried out in an excess of the alkyl mercaptan used as reagent and which also serves as solvent.
- the method according to the invention has the advantage of being able to give a high yield whereas, for this type of reaction, the previous results are weak and of no industrial interest.
- the characterization of the product obtained is carried out by vapor phase chromatography.
- Example 2 By operating as in Example 1 but replacing the triethylamine with ethyldiisopropylamine and by modifying the amount of catalyst (dimethylaminopyridine) and / or the temperature and / or the solvent, the same product is obtained under the conditions and with the results. listed in the table below.
- catalyst dimethylaminopyridine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85420165T ATE45952T1 (de) | 1984-09-14 | 1985-09-11 | Verfahren zur herstellung von o-alkyl-s-(alphaverzweigtes alkyl)alkylphosphonothioate. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8414319A FR2570380B1 (fr) | 1984-09-14 | 1984-09-14 | Procede de preparation de o-alcoyle s (alcoyle ramifie en alpha) alcoyl phosphonothioate |
FR8414319 | 1984-09-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0176456A1 EP0176456A1 (fr) | 1986-04-02 |
EP0176456B1 true EP0176456B1 (fr) | 1989-08-30 |
Family
ID=9307838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85420165A Expired EP0176456B1 (fr) | 1984-09-14 | 1985-09-11 | Procédé de préparation de O alcoyle S (alcoyle ramifié en alpha) alcoyl phosphonothioate |
Country Status (16)
Country | Link |
---|---|
US (1) | US4720565A (ko) |
EP (1) | EP0176456B1 (ko) |
JP (1) | JPS6172795A (ko) |
KR (1) | KR860002521A (ko) |
CN (1) | CN85106788A (ko) |
AT (1) | ATE45952T1 (ko) |
BR (1) | BR8504427A (ko) |
CA (1) | CA1258077A (ko) |
DD (1) | DD236932A5 (ko) |
DE (1) | DE3572667D1 (ko) |
DK (1) | DK416285A (ko) |
ES (1) | ES8604984A1 (ko) |
FR (1) | FR2570380B1 (ko) |
HU (1) | HUT39185A (ko) |
IL (1) | IL76136A0 (ko) |
ZA (1) | ZA857002B (ko) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3838180A (en) * | 1969-11-10 | 1974-09-24 | Gaf Corp | 2-chloroethyl phosphonodithioate esters |
US3751529A (en) * | 1971-06-24 | 1973-08-07 | Monsanto Co | Preparation of esters of phosphorus acids |
AU5706780A (en) * | 1979-04-20 | 1980-10-23 | Commonwealth Scientific And Industrial Research Organisation | Preparation of 0-(4-(hydroxyalkyl)-thiophenyl) organophosphorus esters |
US4362723A (en) * | 1980-12-31 | 1982-12-07 | Rhone-Poulenc Agrochimie | S-Aryl S-(tertiary alkyl) alkylphosphonodithioate insecticides and nematocides |
FR2516517B1 (fr) * | 1981-11-19 | 1986-05-23 | Rhone Poulenc Agrochimie | Derives o-alcoyl et o-aryl s-(tertioalcoyle) alcoylphosphonothioates, leur preparation et leur application |
-
1984
- 1984-09-14 FR FR8414319A patent/FR2570380B1/fr not_active Expired
-
1985
- 1985-08-19 IL IL76136A patent/IL76136A0/xx unknown
- 1985-08-28 US US06/770,214 patent/US4720565A/en not_active Expired - Fee Related
- 1985-09-03 ES ES546666A patent/ES8604984A1/es not_active Expired
- 1985-09-07 KR KR1019850006548A patent/KR860002521A/ko not_active Application Discontinuation
- 1985-09-07 CN CN198585106788A patent/CN85106788A/zh active Pending
- 1985-09-11 DE DE8585420165T patent/DE3572667D1/de not_active Expired
- 1985-09-11 EP EP85420165A patent/EP0176456B1/fr not_active Expired
- 1985-09-11 AT AT85420165T patent/ATE45952T1/de not_active IP Right Cessation
- 1985-09-12 ZA ZA857002A patent/ZA857002B/xx unknown
- 1985-09-12 DD DD85280564A patent/DD236932A5/de unknown
- 1985-09-12 CA CA000490599A patent/CA1258077A/en not_active Expired
- 1985-09-13 BR BR8504427A patent/BR8504427A/pt unknown
- 1985-09-13 HU HU853459A patent/HUT39185A/hu unknown
- 1985-09-13 JP JP60203237A patent/JPS6172795A/ja active Pending
- 1985-09-13 DK DK416285A patent/DK416285A/da not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
ES8604984A1 (es) | 1986-03-01 |
JPS6172795A (ja) | 1986-04-14 |
FR2570380A1 (fr) | 1986-03-21 |
EP0176456A1 (fr) | 1986-04-02 |
ATE45952T1 (de) | 1989-09-15 |
HUT39185A (en) | 1986-08-28 |
BR8504427A (pt) | 1986-07-15 |
IL76136A0 (en) | 1985-12-31 |
KR860002521A (ko) | 1986-04-26 |
ZA857002B (en) | 1986-04-30 |
DK416285D0 (da) | 1985-09-13 |
US4720565A (en) | 1988-01-19 |
ES546666A0 (es) | 1986-03-01 |
FR2570380B1 (fr) | 1987-09-11 |
CN85106788A (zh) | 1987-03-25 |
DK416285A (da) | 1986-03-15 |
DE3572667D1 (en) | 1989-10-05 |
CA1258077A (en) | 1989-08-01 |
DD236932A5 (de) | 1986-06-25 |
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